1,3-bis-(2&#39;-hydroxybenzoyl)-benzenes

ABSTRACT

1,3-BIS-(2&#39;&#39;-HYDROXYBENZOYL)-BENZENES ARE STABILIZERS OF ORGANIC MATERIAL. The compounds are obtained through dealkylating of the corresponding ethers.

United States Patent [191 Brunetti et al. I

I 1 1,3-BlS-( 2- HYDROXYBENZOYL)- BENZENES [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Nov. 3, 1971 [21] Appl. No.: 195,493

Related US. Application Data [63] Continuation-in-part of Ser. No. 878,870, Nov. 21,

1969, abandoned.

[52] US. Cl 260/591, 260/4575, 260/25 BB, 106/188 [51 Int. Cl. C07c 49/44 [58] Field of Search 260/591 June 28, 1974 [56] References Cited UNITED STATES PATENTS 2,773,903 12/1956 Hardy ct 211. 260/591 2,777,828 1/1957 Day Ct :11. 260/591 2,861,053 11/1958 Lappin Ct 211 260/591 2,890,201 6/1959 Hardy 260/591 3,113,121 12/1963 Hoch cl: :1]. 260/591 3,395,115 7/1968 Milionis et a1. 260/591 FOREIGN PATENTS OR APPLICATIONS 1,959,404 6/1970 Germany 260/591 1,959,399 6/1970 Germany 260/591 Primary Examiner-Daniel D. Horwitz [57] ABSTRACT 1,3-bis-(2"hydroxybenzoyl)-ben2enes are stabilizers of organic material. The compounds are obtained through dealkylating of the corresponding ethers.

8 Claims, No' Drawings 1,3-BIS-(2 -HYDROXYBENZOYL)-BENZENES CROSS-REFERENCE This is a continuatio'n-in-part of copending applica-' tion Ser. No.'878,870 filed Nov. 21, 1969 now abandoned.

DESCRIPTION OF THE INVENTION pounds. It has been found that l,3-bis-(2-hydroxybenzoyl)- benzenes of the general formula I R20 -OH OH- -OR1 ll ll 9 wherein I R, and R represent, independently of each other, alkyl having six to 22 carbon atoms, alkenyl having three to 18 carbon atoms or benzyl, alkyl substituted benzyl wherein the alkyl substituent has one to four carbon atoms, or chlorine substituted benzyl and if both of R, and R are carbon atomscontaining radicals, the sum of the carbon atoms inR, and R together is at least 4, and

X represents hydrogen or chlorine.

The alkyl groups denoted in the formula I by R, and R are, e.g., hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl or docosyl groups, whereby the alkyl groups can be branched or unbranched. As alkenyl group, R, and R represent, e.g., the A- or A propenyl group or the A -heptadecenyl group.

If the benzyl group is further substituted by alkyl, it can be a question of the methyl, ethyl, propyl,-butyl or tert. butyl group. I l I If both of R, and R are carbon atoms containing radicals, the sum of the carbon atoms in R, and R together should be at least four, since it is only compounds having at least this number, of carbon atoms in the substituents R, andR which ensure a good compatibility with the substrates.

Particularly suitable as protective agents against light rays are compounds of the formula I, wherein R, and R, represent alkyl having six to 22 carbon atoms, alkenyl having three to four carbon atoms such as, e.g., A propenyl or methallyl groups, or the benzyl group.

Amongst the particularly suitable compounds of the V formula I, thoseare preferred, whereinR, and R, are

identical and represent alkyl having six to 22 carbon atoms, or alkenyl having three to four carbon atoms.

Especially preferred are compounds of the formula I, wherein R, and R are alike and represent alkyl having six to 12 carbon atoms such as the hexyl, octyl, decyl or dodecyl group or R, is hydrogen and R is an alkyl having six to 12 carbon atoms. Compared with simlar protective agents against light rays known hitherto, the new compounds of the formula I are characterised by a low degree of inherent colour, improved fastness to sublimation, better fastness to light and better compatibility with respect to the substrates. These unexpected propterties have especially those compounds of the formula I wherein R, and R are alkyl of from six to 22 carbon atoms. They show particularly a better compatibility with respect to the substrates than similar compounds having as R, and R lower alkyl. The new cmpounds are therefore particularly suitable as protective agents against light rays in the case of substrates which are further processed at elevated temperature.

The compounds in which both R, and R are organic radicals are particularly useful in non-polar substrates such as polyolefines, due to their good compatibility with hydrocarbon substrates. The compounds in which R, is hydrogen on the other hand are particularly valuable as protective agents for polar substrates as used mainly in the coating field. An enhanced compatibility with polar substrates is obtained if R, in such compounds contains a small sumber of carbon atoms.

The new compounds of the formula I are introduced into the light-sensitive carriers or into the light filters in amounts of 0.01 to 30 percent. The amount to be added of the new compounds is governed, amongst other factors, by the thickness of the light filters being produced. For very thin-layers, e.g., in the case of lacquer coatings,,amounts of l to 20 percent are preferred but for thick layers such as, e.g.,. in polymethacrylate sheets, amounts of 0.01 to 1 percent are preferred.

Suitable as carrier materials for the new compounds are primarily organic polymers, both thermoplastic polymers and curable synthetic resins (thermosetting polymers). Thereby applicable are fully synthetic polymers and also natural polymers as well as their polymer-homologous chemical modification products. Appropriate amongst the fully synthetic polymers are pure addition polymers and pure condensation polymers, but also condensation polymers cross-linked by addition polymerisation.

The addition polymers coming into consideration as carrier materials for the new protective agents against light rays, canbe classified under the following main I typs:

l. Homopoly rners and copolymers of vinyland vinylidenemonomers, which are converted by radical, ionic or metal-organic polymerisation initiators into the corresponding polymers. Examples of such monomers, the polymerisates of which are suitable as carrier mate rials are:

Polymerisable, ethylenic, unsaturated halogenated hydrocarbon compounds such as, e.g., vinyl chloride, vinyl fluoride and vinylidene chloride,

polymerisable hydrocarbons with double bonds capable of addition such as, e.g., styrene, isobutylene, ethylene, propylene, l-butene, 3-methyl-l-butene and 4-methyl-l-pentene, whereby both the atactic and the tactic polymerisates apply,

afiunsaturated polymerisable carboxylic acids and their functional derivatives :such as acrylic acid, methacrylic acid, acrylonitrile, alkyl esters and amides of acrylic and methacrylic acid, e.g., the methyl, ethyl and butyl esters of methacrylic acid and acrylic acid,

polymerisable acylderivatives of ethylenic unsaturated alcohols and amines, whereby are suitable acyl radicals of alkane and alkene-carboxylic acids having up to 18 carbon atoms and of aromatic monocyclic carboxylic acids, such as benzoic acids and phthalic acids, as well as acyl radicals of cycliccarbonic acid imides such as, e.g. those of cyanuric acid. Examples are: allyl phthalate, polyallyl melamines, vinyl acetate, vinyl stearate, vinyl benzoate and vinyl maleate, polymerisable polyenes with conjugated double bonds such as butadiene, isoprene, chloroprene, sorbic acid and esters thereof.

2. l-lomoand copolymers of epoxides which are obtained by acidor base-catalytic thermosetting. Suit able in this class are, e.g., the polymerisates of the bisglycidyl ethers of the geminal bis-(p-hydroxyphenyl)- alkanes and cycloalkanes.

3. Homopolymers and copolymers of lactams and lactones such as, e.g., the polymerisates of e-caprolactam or lauryllactam.

4. Homopolymers and copolymers of aldehydes such as, e.g., of formaldehyde and acetaldehyde, such as the polyoxymethylene and the polyoxyethylene.

-5. Reaction products of isocyanates with hydroxyl and/or amino compounds such as, e.g., those of dior polyisocyanates with bivalent or polyvalent hydroxyl or amino compounds. Belonging to this class are also the polyurethanes and polyureas which are obtained by reaction of diisocyanates with polyesters and/or polyethers containing hydroxyl groups.

The condensation polymers suitable as carrier mate rials for the new compounds are, amongst others, polyesters and polyamides. To be mentioned in this respect are linear thermoplastic polyand copolycondensates, which are derived from dicarboxylic acids and organic dihydroxy derivatives or organic diamines, on the one hand, and from hydroxy or aminocarboxylic acid on the other hand. Linear polycondensates are, e.g. the

fibre-forming polymers of w,w-dicarboxylic acids and to, w'-dihydroxy compounds or m,w'-diamines as well as of w-hydroxycarboylic acids or of m-aminocarboxylic acids, which are derived from saturated aliphatic, cycloaliphatic and carbocyclic non-anellated aromatic carboxylic acids.

Suitable for the production of linear condensation products are, e.g., the following components: adipic acid-hexamethylenediamine, sebacic acidhexamethylenediamine, adipic acid/sebacic acidhexamethylenediamine, terephthalic acid-ethylene glycol, terephthalic acid-l,4-dimethylol-cyclohexane, laminodecanecarboxylic acid.

Cross-linked polycondensates as carrier materials are hot-thermosetting'and are obtained, in particular, by condensation of aldehydes with polyvalent condensable compounds. Mention is made of formaldehyde condensates with phenols, ureas and melamines.

Of the condensation polymers cross-linked by subsequent addition polymerisation are the polyester resins. These are polycondensates from'at least one unsaturated organic dicarboxylic acid with polyvalent alcohols, which can be modified with saturated and/or aromatic dicarboxylic acids or their anhydrides and which can be cross-linked by addition of compounds having double bonds'capable of addition. Suitable, for example, as unsaturated dicarboxylic acids are: maleic acid or its anhydride, itaconic acid, citraconic acid or fumaric acid; suitable as saturated dicarboxylic acids are the succinic, adipic, azelaic or sebacinic acids, as aromatic dicarboxylic acids the isophthalic acid or the anhydrides of the phthalic, tetrachlorophthalic or tetrabromophthalic acids and l,2,3,4,7,7- hexachlorodicyclo-(2,2,l )-hept-2-ene-5,6-dicarboxylic acid anhydride; suitable as alcohols are ethylene, propylene, diethylene, neopentyl glycol or trimethylpentanediol, and suitable as cross-linking agents are styrene, p-chlorostyrene, diallylphthalate, methylmethacrylate, vinyl toluene or diallylcyanurate.

The natural polymers, suitable as carrier materials for the new protective agents against light rays, are, e.g., polysaccharides, such as cellulose or also rubber and proteins.

Amongst the polymer-homologous, chemically modi fied synthetic polymers are, e.g., the reaction products of polyvinyl alcohols with aldehydes such as polyvinyl butyral, and the saponiflcation products of polyvinyl esters. Polymer-homologous, chemically modified natural polymers, as carrier materials for the new protective agents against light rays are, e.g., the cellulose esters and cellulose ethers, such as the cellulose esters of the acetic acid, propionic acid, benzoic acid with, on average, 1 to 3 acyl groups per unit of glucose.

.The above listed polymers can also be used in the form of mixtures, as carriers of the new protective agents against light rays in the compositions according to the invention.

Particularly valuable compositions, according to the invention, contain, as carriers of the new protective agents against light rays, light-sensitive polymerisates which are derived from styrene, vinyl chloride, vinyl fluoride, acrylonitrile, olefins, acrylic acid esters and/or methacrylic acid esters, as well as polyesters, polyamides, polyester resins, polyacetals, polycarbonates, polyurethanes, cellulose ethers and cellulose esters. Especially preferred carriers are polymeric hydrocarbons such as, e.g., highand low-pressure polyethylene, polypropylene, polybutene, poly(-3-methyll -butene), poly(4-methyl-1-pentene), ethylene-butene copolymers, ethylene-propylene copolymers, ethylene-propylene-terpolymers, propylene-ethylene-polyallomers.

Also suitable as carriers, in addition to these polymers, are natural as well as synthetic light-sensitive waxes, fats and oils, and also complex systems such as photographical material, emulsions containing lightsensitive fatty substances, emulsions or dispersions of the aforementioned polymers.

The molecular weight of the aforestated polymers is of secondary importance, providing that it is within the limiting values required for the characteristic mechanical properties of the polymers concerned. Depending on the polymers, it can be 1,000 to several millions.

The incorporating of the new compounds into these polymers is effected, e.g., depending on the nature of the polymers, by the introducing of at least one of these compounds, and optionally further additives, into the melt, according to methods normally applied in practice, before or during moulding, or by dissolving them in the corresponding monomer before polymerisation, or by dissolving of the polymer and/or the additives in solvents and subsequent evaporation of the latter. Further additives are, e.g.:

Antioxidising agents such as 2,2-thiobis-(4-methyl-6-tert.butylphenol); 4,4- tiobis-(3-methyl-6-tert.-butylphenol); 2,2-methylene-bis-(4-methyl-6-tert.butylphenol); 2,2 -methylenebis-(4-ethyl-6-tert. butylphenol); 4,4-methylene-bis- (2-methyl-6-tert.butylphenol); 4,4-butylidene-bis-(3- methyl-6-tert.butylphenol); 2,2-methylene-bis-[4- methylacetophenoneoxime;

methyl-6-(a-methylcyclohexyl)-phenol]; hydroxy-3-tert.butyl-5'-methylbenzyl)-4- methylphenol; l,l,3-tris-(4-hydroxy-2 '-methyl-5 tert.butylphenyl )-butane; 1,3 ,5trimethyl-2,4,6-tri- (3',5-ditert.butyl-4'-hydroxybenzyl)-benzene; esters of the B-4-hydroxy-3,5-ditert.butylphenyl-propionic acid with monoor polyvalent alcohols such as methanol, octadecanol, hexanediol, trimethylolethane or pentaerythrite; 2,4-bis-octylmercapto-6-(4-hydroxy- 3,SditertbutyIaniIion)-s-triazine; 2,4-bis-(4-hydroxy- 3,5-ditert.butylphenoxy)-6-octylmercapto's-triazine; l, l -bis-(4-(4-hydroxy-2'-methyl-5 '-tert.butyl)- phenyl-3-dodecylmercapto-butane; 4-hydroxy-3,5- ditert. butylbenzyl-phosphonic acid ester such as the diethyl-or dioctadecyl-ester; (3-methyl-4-hydroxy-5- tert. butylbenzyl)-malonic acid-dioctadecyl ester; S- (3,5-dimethyl-4-hydroxybenzyl)-thioglycolic acid octadecyl ester; phenyl-l-naphthylamine; phenyl-2- naphthylamine; N,N-diphenyl-p-phenylenediamine; N,N'-di-2-naphthylp-phenylenediamine; N,N'-disec.butyl-p-phenylenediamine; 6-ethoxy-2,2,4-

trimethyl-l,2 -dihydroquinoline; 6-dodecyl-2,2,4- trimethyl-l,2-dihydroquinoline; mono and dioctyliminodibenzyl; polymerised 2,2,4-trimethyl-l,2-

dihydroquinoline.

LIV-absorbers and protective agents against light rays such as 2-(2-hydroxyphenyl)benzotriazoles, e.g., the 5-methyl-, 3',5-ditert.butyl-, 5'tert.butyl-, S-chloro- 3, 5'-ditert.butyl-, 5-chloro-3'-tcrt.butyl-5'-methyl-, 3',5'-ditert.amyl-, 3'-methyl-5'-B-carhomethoxyethyl-, S-chlorofi',5-ditert.amylderivative; 2,4-bis-(2'- hydroxyphenyl)-b-alkyl-s-triazines such as the o-ethylor 6-undecyl-derivative; 2-hydroxy-benzophenones such as the 4-hydroxy-, 4-methoxy, 4-octoxy, 4- decyloxy-, 4-dodecyloxy-, 4,2,4'-tri-h'ydroxyor 2'- hydroxy-4,4'-dimethoxy-derivative; phenylsalicylate; octylphenylsalicylate; benzoylrecorcin; dibenzoylresorcin', a-cyano-B-B-diphenylacrylic acid ethylor isooctyl ester; a-carbomethoxycinnamic acid methyl ester; a-cyano-[3methyl-p-methoxycinnamic acid methylor butyl ester; N-(B-cyano-B-carbomethoxy-vinyl)-2- methyl-indoline; nickel complexes of the 2,2thiobis- (4-ditert.octylphenol), such as the 1:1 and 2:1 complex, optionally with, other ligands such as nbutylamine; nickel dibutyldithiocarbamate; nickel salts of 4-hydroxy 3,5-di-tert. butylbenzylphosphonic acid monoalkyl esters such as the methyl, ethyl or butyl ester, the nickel complex of the 2-hydroxy-4- 4,4-dioctyloxyoxanilide 2,2'-di-octyloxy-5,5-ditert.butyloxanilide; 2,2-didodecyloxy-S ,5 '-ditert.butyloxanilide.

Metal deactivating agents such as monoand dihydrazides of monobasic and polybasic acids such as oxalic, adipic, salicylic, terephthalic or isophthalic acid; substituted oxamides and oxanilides; N-salicyloyl-salicylaldehyde-hydrazones; n-butylbenzotriaaolc; tetrahydrobenzotriazole; 2-guanidinobenzo-- imidazole.

Nucleating agents such as 4-'tert.butylbenzoic acid, adipic acid, diphenylacetic acid.

Peroxide decomposing compounds such as esters of the B-thiodipropionic acid, e.g., the lauryl, stearyl, myristyl or tridecyl ester; salts of the 2-mercaptobenzoimidazole, e.g., the zinc salt; diphenylthio-urea; triphenyl phosphite; diphenylalkyl phosphites: phenyldialkyl phosphites; trinonylphenyl phosphite; trilauryl phosphite; trioctadecyl phosphite; 3,9-diisodecyloxy- 2,4,8 l 0-tetraoxa-3,9-diphosphaspiro-( 5 ,5 )-undecane; tri-(4-hydroxy-3,iditertbutylphenyl)-phosphite.

Other stabilisers such as potassium, barium, cadmium, magnesium, calcium or zinc salts or organic acids, e.g., stearates or laurates; basic or neutral lead salts of organic or inorganic acids; tin-containing stabilisers such as dibutyl tin laurates, -maleates or -mercaptides; hexamethylphosphoric acid triamide; copper salts such as copper acetates or copper lor copper llhalides, optionally in combination with alkali halides, -hydrophosphites, -phosphites and phosphates or free phosphorous or phosphoric acid; manganese ll-salts such as the chloride, hypophosphite or phosphate, optionally in combination with other hypo'phosphites, phosphites and phosphates; dicyanodiamide; diphenylurea;

Other additives such as softeners, antistatics, flameproofing agents, pigments, soot.

Inorganic fillerssuch as, e.g., asbestos, glass fibres, kaolin, talcum.

The new protective agents against light rays can also be applied to polymer granulate and to thinner carrier structures,.such as to films or threads, from baths, e.g., from aqueous dispersions or from solution in organic solvents.

The light-sensitive materials can, moreover, be protected from the harmful action of light by being coated with a protective layer, e.g., with a lacquer, containing at least one defined compound of the formula I, or by being covered with materials, such as films, disks or sheets, which contain such protective agents against light rays. In these two cases. the amount of the added protective agent against light rays is advantageously [0 +percent (relative to, the protective-layer material) for protective layers of less than 0.01 mm thickness, and 1 10 percent for protective layers of 0.01 to 0.] mm thickness.

In the case of certaintypes of application, especially where a warm plastic granulate is powdered with protective substances, products are especially valuable which melt above the softening temperature of the particularpolymer, and which nevertheless are sufficiently soluble in the melted polymer.

The new compounds of the general formula 1 are produced, e.g., by reacting a compound of the general-formula Ia HO- -OH Hb- -OH 0 0 ll ll 0 o with l or 2 equivalents of an alkylating agent.

e.g., alcohols, ketones, dimethylacetamide or mixtures thereof with water, at temperatures of 20 150C, preferably 40 120C.

The compounds of the general formula I can also be obtained by reacting, by methods known per se, isotion, the reaction mixture changes from an oily suspension to a suspension of solid particles. The internal temperature of 70 is maintained for 45 minutes until the main reaction has subsided and the reaction is comphthalic acid chloride or S-chloroisophthalicacid pleted during 1 hour with an internal temperature of chloride, in the present of Friedel-Crafts catalysts, 80. After cooling the mixture, decomposition is per wich resorcin monoor -dialky1'ethers. The following formed with acidified ice water and the solvent is recompound can, for example, be used: resorcin dihexyl moved by steam distillation. After washing with disether. tilled H 0 and drying of the reaction product, recrystal- With the use of resorcin dialkyl ethers, especially in 10 lisation is repeatedly carried out from methyl cellosolve heating to higher temperatures, there usually very readand 1,3-bis(2-hydroxy-4'-methoxy-benzoyl)-benzene ily occurs a dealkylation of the alkoxy groups which are is Obtained as light-yellow crystals having a melting in the o-position to the carbonyl groups. These com- Point Of l65l66. pounds can be further dealkylated to a compound of A 332 nm, e 19,300 the formula I wherein 1 is hydrogen B 255.9 g of 1,3-bis(2-hydroxy-4-methoxy- The compounds of the general formula I can also be benzoyl)-benzene are suspended in 2,500 ml of anhy obtained by reacting, in a manner known per se. e.g., drous benzene and to the suspension are added in porisophthalic acid chloride with resorcin monoalkyl tions, at room temperature, 550gof powdered aluminethers, to give di-esters and transposing these, in the ium chloride. The whole is heated, whilst being stirred, presence of Friedel-Crafts catalysts, preferably alumiuntil refluxing is obtained. This temperature is mainnum chloride, to the desired compounds which can be tained for 2 hours and, after cooling the mixture with further dealkylated to compounds of the formula I ice water/HCl, decomposition is carried out. The solwherein R is hydrogen, vent is removed by steam distillation, the fine-grained The following examples illustratethe invention. The yellow reaction Product is filtered thoroughly temperatures are given in degrees Centigrade and the washed with hot water and dried. After recrystallisation absorptivity (a) is defined as follows: fr m n l/ ,3- i y ybenzoyl)-benzene is obtained as light-yellow crystals Flog a having a melting point of 215216 whereby A max 325 2 1,, represents the intensity of the incident light, g of 1 y y' Y I represents the intensityof the emergent light, are dissolved in 150 ml of methanol, g o 0 represents the concentration of absorber in methylat? are added the solution is concentrated y grams per litre of chloroform or dimethyl formamide evaPoratlon and h l f dissolved l 500 ml 1 percent of acetic acid, and 35 of drmethylacetamlde. Whrst stirring the SOlUt101'l,'27.4 d represents the layer thickness penetrated by rays in of l'bromobutzflle r added dropwlse at 2 9 cm. and, after the addition is completed, the reaction mix- EXAMPLE 1 ture is heated for 4 hours to 80. After cooling, the reaction mixture is stirred into 1,500 ml of ice water A. 304.5 g of isophthalic acid dichloride are dis- 40 slightly acidified with HCl, the obtained precipitate solved at 510 in 3,600 ml of 1,l,2,2- taken up in ether, the organic phase dried with sodium tetrachloroethane and to the solution are added in porsulphate and the ether expelled. The residue is taken up tions, at temperatures below 10, 412 g of commercial in toluene and, as preliminary purification, repeatedly powd re l minium chloride. T h light-yellow sustreated hot with fuller's earth. After the solvent has pension are added dropwise within 30 minutes, with been expelled, the residue is recrystallised from acetostirring and cooling of the suspensionto 5-l0, 414 g nitrile and the 1,3-bis-(2-hydroxy-4-butoxy-benzoyl)- of resorcin dimethyl ether. The reaction mixture is benzene is obtained in the form of light-yellow crystals, gradually heated, whilst being stirred, to internal M.P. 114-115. temperature. At about 60 internal temperature, the A 332 nm, e 21,600 initially clear red colour of the reaction solution 50 if, instead of l-bromobutane, the equivalent amount changes to a yellowish-orange colour and, with simultaof other suitable halogen compounds are used, with neously occurring clouding, the splitting off of hydrootherwise the same procedure, the compounds listed in chloric acid commences. During the course of the reac- Table l are Obtained.

TABLE I no 01[ no -()lt -C -(J Alison: )1 J| tlvlly Alkylation agent 1t 1 (nm,) a

l-bromoethane Ethyl 1111- 3150 [11.11 l-bromopropane Propyl 14514 11513 511.4 2-br0mopr0pane Isopropyl.. ..m. -121 3152 50.3 l-chloropentanm. HlHllJ 21112 43. 3 l-bromohexane... (ll) :53). 40. .1 l-bromooctane. ltesln 331 ml. 2 1-ch1orod0decane.. 134-415 333 '62. H l-chlorooctadecane Octadecyl 7 333 15,34 1-ch1or0-3,3-dimethyl propane"... 3,3-dimethylpropy1. lift- J6 332 44.5 1-ch10r0-3,3-dimethy1 butane 3,3-dimethylbutyL. 141442 332 4151" 1- ch10r0-2-methyl propene2. 2-methylptopenyl-2 1211- 3512 45.2 Benzyl chloride Benzyl 3- J 4-tert.-buty1-benZy1-eh1oride 4-tert.-buty1-benzy1 3-52 56.8

EXAMPLE 2 203 g of isophthalic acid dichloride are dissolved at 5 in 1,800 ml of nitrobenzene and to this solution are added in portions, at temperatures below 10, 275 g of powdered aluminium chloride. Into the reaction solution are then added dropwise within 30 minutes, with stirring and cooling to 5 10, 332 g of resorcin diethyl ether and, after the addition is completed, the internal temperature is gradually raised to 70, whereby at about 60 the splitting off of HCl commences. The main reaction at approximately 70 internal temperature is allowedto subside and the temperature is then raised to 80 to complete the reaction over 1 hour. After the mixture has cooled, decomposition is performed with ice water/HCl and the nitrobenzene removed by steam distillation. After recrystallising the reaction product from acetonitrile, the 1,3-( 2'- hydroxy-4'-ethoxy-benzoyl)-benzene is obtained in the form of light-yellow crystals having a melting point of 99 100.

A "m =330 nm; e 20,000

By using, instead of resorcin diethyl ether, equivalent amounts of resorcin dipropyl ether or resorcin dibutyl ether, with otherwise the same procedure, 1,3-bis-(2- hydroxy-4'-propoxy-benzoyl)-benzene or 1,3-bis-(2'- hydroxy-4'-butoxy-benzoyl)-benzene is obtained.

EXAMPLE 3 mixture is heated in the course of minutes to 70 internal temperature, whereby at about 60 the evolution of HCl commences. Simultaneously, the initially practically homogeneous reaction solution changes by way of an oily suspension into a suspension of semisolid particles. The temperature is maintained at 70 for 1 hour, or until the main reaction has subsided, the internal temperature is raised to 80 and the reaction completed during 1 hour. After cooling, the reaction mixture is decomposed with ice water/HCI and the solvent expelled by steam distillation. After the washing and drying of the reaction product, it is recrystallised from ethylene glycol monomethyl ether and the 1,3- bis-(2 -hydroxy-4-methoxy-benzoyl )-5-chlorobenzene is obtained in the form of yellow crystals which melt at 170 171.

If, instead of resorcin dimeth yl ether, equivalent amounts of the resorcin ethers, listed in Table II, are used, with the procedure being otherwise the same, the compounds given in Table II are obtained.

benzoy1)-5-ch10robenzene.

B. 206.4 I g of 1,3-bis-(2'-hydroxy-4-methoxybenzoyl)-5-chlorobenzene are suspended in 2,000 ml of anhydrous benzene and to the suspension are added in portions, at room temperature, 400 g of powdered aluminium chloride. The reaction mixutre is heated, whilst being stirred, until refluxing occurs and the temperature is maintained there for 2 hours. After cooling, the reaction mixture is decomposed with ice water/HCl and the solvent expelled by steam distillation. The obtained reaction'product is washed with hot water. After drying and recrystallising from methanol/water, the 1,3-bis-(2', 4'dihydroxybenzoyl)1-5-chlorobehzene is obtained in the form of yellowish-white crystals, which melt at 134.

A 330 nm; e= 20'700 C. 38.5 g of 1,3-bis-(2,4'-dihydroxy-benzoyl)-5- chlorobenzene are dissolved in 150 ml of methanol, 11.8 g of sodium methylate are added, the solution is concentrated by evaporation and the residue again dissolved in 550 ml of dimethylacetamide. Whilst the solution is stirred, 27.4 g of l-bromobutane are added dropwise at 20 40 and, after completion of the addition, the reaction mixture is heated for 4 hours to After cooling, the reaction mixture is stirred into 1,500 ml of ice water, slightly acidified with HCI, and the precipitated reaction product is taken up in ether. After the ethereal solution has been dried, the ether is evaporated off, the residue repeatedly treated hot in toluene solution with fullers earth and the solvent removed. After recrystallisation of the evaporation residue, the l,3-bis-( 2'hydroxy4'-butoxy-benzoyl )-5- chlorobenzene is obtained in the form of light-yellow crystals.

)t m 334 nm; e= 29'900 1f, instead of l-bromobutane, equivalent amounts of the alkylation agents in Table III are used, proceeding otherwise in the same manner, the compounds listed in Table III are obtained.

propene propenoxy )-henzoyl l-S-chlorobenzene EXAMPLE 4 A. 350 g of 1.3-bis-(2,4-dihydroxy-benzoyl)- benzene, 5 g of potassium iodide and 190 g of l- EXAMPLE 5 A solution of 15 g of acetyl cellulose with, on averbromododecane are dissolved in 1,000 ml of dimethyl- 5 age, 2,5-acetoxy groups per glucose unit, and 0.075 g acetamide and, whilst being stirred, heated to 85. At this temperature, a solution of 49 g of potassium hydroxide in 50 ml of water is added dropwise in the course of 2 hours and, after completion of the addition, the solution is allowed to fully react during a further 3 hours at 90. The reaction solution is subsequently stirred into 2 litres of acidified ice water and the precipitated reaction product taken up in ether. After drying of the ethereal solution, the ether is evaporated off and the evaporation residue stirred up with 700 ml of ethaobtained results are given in the following Table V. nol. After cooling and trituratlon, the l,3-bis-(2'- T bl V hydroxy-4-dodecyloxy-benzoyl)-benzene, forming as a 6 by-product, precipitates out, is filtered off and subsequently washed with a little cold ethanol. 700 ml of g gq Pr in C water are then gradually added, while stirring proceeds, uv-gbsor iilis aer to the filtrate, whereby, after cooling and trituration, exposure the reaction product gradually crystallises out. After Range: 300440 drying and recrystallisation twice from toluene, the 90 l-(Z ethoxy-benzoyU-bengene 4-dihydroxy-benzoyl)-3-(2"-hydroxy-4"-dodecyloxyb y 1 gy- P 5 poxyenzoy enzene benzoyl)-benzene 1s obtalgied 1n the form of whitish c 1ibis. hydmxy 4. pcmoxy 93 crystals Wl'llCh melt at 137 138 benzoyl)-benzene A m 332 1900 d 1,3-bis-(2hydroxy-4'-octoxy- 93 1 I I ,1 benzoyl) -benzene B. 51.23 g of (2 ,4 -d1hydroxy-benzoyl)-3-(2 e 94 hydroxy-4 -dodecyloxy-benzoyl)-benzene, 1 g of podecyloxy:ben;oy|);ben;ene tassium iodide and 13.7 g of l-bromobutane are dis- 1??" g l 96 solved in 150 ml of dimethylacetamide and heated to g g g nzoy 80. To this solution is then added dropwise, in the g 1,3-bis-[2hydroxy-4'-(3", 3"- 96 course of 2 hours, a solution of 6.6 g of potassium hyglmeihylbutoxyl-benmyllenzene droxide m 10 ml of water and, after the addition 18 corn; h |,3 bi .(2-hydroxy 4'-b ItOXy- 92 pleted, the whole 15 heated for a further 3 hours to 90 benzoyl) 5-chloro-benzene The reaction solution is stirred into 500 ml of acidified g 4g- 95 ice water and the precipitated reaction rpoduct taken 233,?" anzoy up in ether. After drying of the ethereal solution with j 1,3-bis-(2'-hydroxy-4'-benzyl 94 sodium sulphate, the ether is evaporated off and the 40 P s'd w'th th ddition of active charcoal e eatk H2 ihydroxy'it 'propoxy' 92 re 1 1 e a p benzoyl)-3-(2"-hydroxyedly recrystalllsed from an alcohol/acetone m1xture, 4"-dodecyloxy-benzoyl)- a ..u .0. benzene \talvhgrebygh edl ((12 hlydrogty 4 b1 tbxy benzoy I) 3 (2 d I H2LhwlrowAkPemow 93 y roxyo ecy oxyenzoy enzene rso tame b y] -3(2"-hydroxy- MP. 65 66. 7 4"-dodecyloxy-benzoyl)- A 333 nm; e 20800 m l i g g 4, be" I 90 If, instead of l-bromobutane, the alkylation agents n g lgf L ilQQ-Y' given in Table IV are used, with otherwise the same 4"-dodecyloxy-benz0yl)- procedure, then the compounds listed in the table are benzene obtained. 4

Table IV Acylation Compound A Absorbagent (nm) tivlty l-bromopropane 1-(2-hydroxy-4'-propoxybenzoyl)-3 332 37.5

(2"-hydroxy 4-dodecyloxybenzoyl)- benzene l-bromopentane l-(2'-hydroxy-4-pentoxy-benzoyl)3- 333 35.3

(2"-hydroxy4"-dodecyloxy-benzoyl)- benzene l-chloro-3,3 dil-[2'-hydroxy-4'-(3", 3"-dimethyl-butoxy)- 333 34.8 methyl butane benzoyl]-3'(2"'hydroxy-4"'-dodecyloxyhenzoyU-bcnzene 1-bromodecanc l-( 2'-hydroxy-4-dccyloxy-benzoyl)-3- 332 31.9

' (2"-hydroxy-4"-dodccyloxy-benzoyl)-bcnzene lbromooctadecane l-(2'-hydroxy-4'-octadccyloxy benzoyl)-3- 333 27.4

2-hydroxy-4"-dodccyloxybcnzoyl)henzenc benzyl chloride l-(2'-hydroxy-4'-bcnzyloxy-bcnzoyl)-3- 333 34.4

EXAMPLE 6 Difficultly inflammable, liquid polyester resin is polymerised at 80, after addition of 0.25 percent by weight of a UV-absorber in Table V] with l percent by weight of benzoyl peroxide, to form 2.5 mm thick plates. The plates are subsequently cured at 120. Plates thus produced and exposed to light exhibit appreciably less browning than plates similarly exposed to light but produced without the aforementioned UV- absorbers.

The polyester resin used was produced as follows: A mixture of 343 g of maleic acid anhydride and 428 g of tetrachlorophthalic acid anhydride is added in portions at 80 to a mixture of 170 g of ethylene glycol and 292 g of diethylene glycol. After displacement of the air in the reaction vessel by nitrogen, the temperature is raised within one hour to 150, then within 9 hours to 210 and thereafter this temperature is maintained for a further hour. The mixture is then cooled to 180, the vessel is put under vacuum and the pressure slowly reduced to 100 Torr. These conditions are maintained until the acid number of the reaction mixture has fallen to below 50.

100 g of the thus obtained polyester are mixed with 50 g of styrene and the mixture is polymerised under the aforementioned conditions.

Similar results are obtained if, instead of the tetrachlorophthalic acid, the equivalent amount of phthalic acid anhydride is used, although in this case the resulting polyester'resin is not difficultly inflammable.

If, in the above described process, the styrene is replaced by methyl methacrylate, then plates are obtained which are, in themselves, less prone to browning and which, moreover, are more easily stabilised.

Example 7 100 parts of methacrylic acid methyl ester, 0.5 parts of a UV-absorber from Table VII and 0.2 parts of lauroyl peroxide are mixed together andpolymerised at a temperature of 50 70 in the form of plates of 2 mm thickness.

As can be seen from thefollowing table, such plates can be employed as UV-filters.

Table VI No. UVAbsorber it transmission Loss of with 44.0 nm transmission before exposure with 440 nm after 1000 hours Fade'O-Meter exposure none 88 3| :1 l,3-bis-(2"hydroxy-4-propoxy-benzoyl)- 88 2.l

benzene b l,3-bis-(2"hydroxy-4'-butoxy-benzoyl)- 87 2.0 benzene c l,3-bis-(2'-hydroxy-4'-0ctoxy-benzoyl) 88 4.5

benzene d l,3-bis(2'-hydroxy-4'-dodecyloxy-ben- 88 3.5

zoylybenzene e l,3bis-(Z' hydroxy-4"octadecyloxy- 88 4.5

benzoyl)-benzene f l,3-bis-[2-hydroxy4'-(2"-methyl-pro- 87 L9 penoxy)-benzoyl]-benzene g l,3-bis-(2'-hydroxy 4-benzyloxy-benz- 88 3.7

oyl-benzene h l.3-bis-(2"hydroxy-d"butoxy-benzoyl)- 87 2.2

5 chlorobenzene i l,3'bis( 2 '-hydroxy-4'-dodecyloxy benz- 87 3 .7

oyl)-5-chlorobenzene l-(2'-hydroxy-4'-ethoxy-benzoyl)-3-(2'" 88 4.1 hydroxy-4"dodecyloxy-benzoyl)-benzene k l-(2-hydroxy-4-butoxy-benzoyl)-3- 88 4.2

(2"-hydroxy 4"dodecyloxy'benzoyl)- benzene I l-(2'-hydroxy-4'-octoxy-benzoyl)-3 87 4.2

(2"-hydroxy-4"-dodecyloxy-benzoyhbenzene Table VII No. UV'Absorber transmission of light of the wave length 340 nm 430 nm none 86 92 a l,3-bis (2'-hydroxy4'ethoxy-benzoyl)- 2 92 benzene b l,3-bis(2'-hydroxy-4'-butoxy-benzoyl)- 2 92 benzene c l,3-bis-[2'-hydroxy-4'-(3", 3"-dimethylbut- 2 92 oxybenz'oyll-benzene d l,3-bis-(2"hydroxy-4'-heptoxy-benzoyl) 2 92 benzene e l,3-bis-(2-hydroxy4' dodecyloxy-benzoyl)- 2 92 benzene f l,3-bis-(2-hydroxy-4'-octadecyloxy- 2 92 benzoyU-benzene g l,3'bis-(2'-hydroxy-4benzyloxy-benzoyl)- 2 92 benzene h l S2'-hydroxy-4isopropcxy-benzoyl)-3- 2 92 (2 '-hydroxy-4"dodecyl-benzoyl)-benzene i l-(2'-hydroxy-4'-hexoxy-bcnzoyl)-3-(2"- 2 92 hydroxy-4"-dodecyloxybenzoyl)-benzene j l-(2'-hydroxy-4 octadecyloxy-benzoyl)-3- 2v 92 (2"-hydroxy-4' '-dodecyloxy-benzoyl)benzene Example 8 Films'are produced in the usual manner on a tworoller mill from a mixture of:

100 parts of suspension polyvinyl chloride (K-value 16 EXAMPLE 9 l parts of polyethylene with a density of 0.917 are homogeneously mixed at 180 in the Brabender- Plastograph with 0.5 parts of a UV-absorber from 60), Table x and 0.5 parts of 3- 3', 2.5 parts of a dialkyl tin mercaptide stabiliser (Ad- 5-di-t.butyl-4-hydroxy-phenyl)-propionic acidvastab 17 M from the Deutschen Advance Produkoctadecyl ester. The thus obtained mixture is pressed tion Ghbl-l, Germany) in a platen press at 165 to form 1 mm thick plates. 1.0 part of an epoxy stabiliser (Advaplast 39 from the These plates exhibit after weathering, in the case of aforementioned firm) 1O bending around 90, appreciably less proneness to britl.0 part of a wax, employed as lubricant and processtleness than plates without the addition of the additives ing auxiliary agent (Wax E from the firm Farbwerk in Table X.

Table Vlll Appearance UV-Absorber of the exposed specimen none dark brown discolouration the whole specimen somewhat yellowish commencement of yellowing at isolated places 0 l,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)- isolated yellowishbrown areas at a few places. yellowishbrown discolouration yellowish g l,3-bis-( 2 -hydroxy-4'-dodecyloxy-benzoyl S-chlorobenzene slightly yellowish at isolated places commencement of yellowing at isolated points Hoechst, Germany) and 0.2 parts of a UV-absorber from Table Vlll. Specimens of these films are exposed for 2,000 hours in the Xenotest exposure apparatus and tested with respect to discolourations.

The results are given in Table Vlll lf, instead of the aforementioned mixture, the following recipe is used:

100 parts of suspension polyvinyl chloride (K-value 1.2 .parts of a barium-cadmium soap (Mark WS from the SA. Argus Chemical N.V., Belgium),

0.5 parts of an organic phosphite (Mark C from the above firm) 1.0 part of a wax (Wax E from Farbwerke Hoechst, Germany) and 0.2 parts of a UV-absorber from Table lX,

with otherwise the same procedure, the results given in Table IX are obtained.

Table IX Table X UV-Absorber l 1 l 1 t l l l l 1 Appearance of UV-Absorber the exposed specimen none severe browning of the entire specimen a l.3-bis-(2'-hydroxy4'-propoxybenzoyl)-benzene at isolated places a little yellowish somewhat yellowish slight touch of yellow yellowish discolouration at isolated places yellowish discolouration EXAMPLE tleness than plates produced otherwise in the same manner, but without addition of the protective agents against light rays given in Table XI.

Table Xl UV-Absorber -bis-( 2 '-hydroxy'4'-butoxy-benzoyl )'benzene -bisll'-hydroxy-4"( 3", 3"-dimethylpropoxy)-benzoyl l l l l l l l 1,3-bis-( 2 '-hydroxy-4 '-hexoxy-benzoyl)-benzene l,3-bis- [2'-hydroxy-4'-(3", 3"-dimethylbutoxyrbenzoyl l EXAMPLE 11 100 parts of polystyrene granulate are mixed dry with 0.3 parts of a protective agent against light rays from Table X11 and 0.1 parts of 2,4,6-tri-t.-butyl-phenol and the mixture is sprayed with an injection-moulding ma-' chine to form 2 mm thick plates.

The obtained plates are exposed for 1,000 hours in the Xenotest apparatus and subsequently the yellowing of the plates is determined by means of the yellowing factor in the following manner:

Y.F. T 42 e udion/T(560 whereby AT represents the transmission loss occurring during exposure with the wave-lengths 420 and 680 nm and T(560) represents the transmission value in percent of the unexposed specimen in the case of 560 nm.

Table X11 Table X11 Continued g l,3-bis-(2-hydroxy-4'-benzyloxy-benzoyl)- 3.1

benzene h 1-(2-hydroxy4-butoxy-benzoyl)-3 (2"-hydroxy- 2.5

4 '-dodecyloXy-benzoyU-benzene i 1-(2 '-hydroxy-4-hexoxy-benzoyl13-3(2-hydroxy 3.1

4 '-dodecyloxy-benzoyU-benzene 1-(2-hydroxy 4'-decyloxy-benzoyl)-3-(2"- 3.4

hydroxy-4 '-dodecyloxy-benzoyl)benzene EXAMPLE l2 Bleached maple-veneer is coated with a wood varnish having the following composition:

parts by weight of cellulose acetate (of the firm Bayer in Leverkusen. Germany) with ca. 56% acetic acid content, parts by weight of dimethyl glycol'phthalate; part by weight of 1 l,B-bis-I2'-hydroxy 4'-dodecyloxy benzoyll-benzene parts by weight of methyl alcohol, parts by weight of toluene and parts by weight of eth'ylacetate.

The natural yellowing of the wood is retarded by this varnish.

EXAMPLE 13 A cosmetic protective agent against light rays is obtained as follows:

5 parts of white ceresine wax 22 parts of white petrolatum 19.5 pans of white mineral oil 15 parts of lanoline anhydrous 2 parts of l,3-bis-[2'-hydroxy-4-l1exoxy-benz0yl]-benzene 36 partsof water 0.5 parts of perfume.

The ceresine, petrolatum and lanoline are melted together and the protective agent against light rays dissolved in the melt. The mineral oil is then added at and tle water is subsequently slowly stirred in at the same temperature. Stirring is continued until the temperature has fallen below 50, whereupon the perfume is added.

EXAMPLE 14 A sprayable cosmetic protective agent against light rays is obtained by dissolving in parts of ethanol, 10 parts of ricinic acid methyl ester, 10 parts ofoleyl alcohol and 1 part of 1,3-bis-[2'-hydroxy-4'-hexoxybenzoyl]-b enzene. After addition of commercial fluorine-containing propellants (e.g., Freon products of the firm Du Pont, USA), the solution can be sprayed from an aerosol container.

EXAMPLE 15 35 g of l,3-bis-(2,4--dihydroxy-benzoyl)-benzene are dissolved in ml of metahnol and to the solution are added 5.9 g of sodium methylate. The solution is dried and the residue again dissolved in 500 ml of dimethylacetamide. Whilst the solution is being stirred, 16.5 g of l-bromohexane are added dropwise at 20 40 and, after the addition is completed, the reaction mixture is heated for 4 hours to 80. After cooling of the reaction mixture, it is stirred into ice water, which is slightlyacidified with hydrochloric acid, the obtained precipitate taken up in diethyl ether, the ethereal solution dried and the ether distilled off. The residue is taken up 5 in toluene and repeatedly treated in the hot state with fullers earth. After the solvent has been distilled off, the residue is treated in the hot state with hexane, whereby unchanged starting product remains behind. After concentration by evaporation of the hexane solution, 10 the residue is recrystallised from xylene and the l-(2,4- dihydroxy-benzoyl )-3-( 2 -hydroxy-4 -hexyloxybenzoyl)-benzcne is obtained in the form of faintly yellow crystals, M.P. 134 135. A,,,,,,= 332 nm, e 19,2- 00.

Byusing, instead of l-bomohexane, the equivalent amount of 'the alkylating agents which are given in Table XIII, with otherwise the same procedure, the compounds listed in Table XIII are obtained.

TableXlII Absorp- Alkylating A tivity agent Compound nm a l-bromol-(2,4-dihydroxy-benzoyI)-3-(2-hydroxy4-butoxy-benzoyl)- 332 47.2

butane benzene l-chlorol-(2,4-dihydroxy-benzoyl)-3-(2 -hydr0xy-4 -octoxy-benzoyl)- 333 4 l .8

octane benzene l-chlorol-(2,4dihydroxy-benzoyl)-3-(2'-hydroxy-4-dodecyloxy- 332 36.7

dodecane benzoyltbenzene l-bromol-(2,4-dihydroxy-benzoyU-3-(2'-hydroxy-4'octadecyloxy- 332 32.0

octabenzoyl)-benzene decane benxyl 1-(2,4-dihydroxy-benzoyl)-3-(2-hydroxy-4'-benzyloxy- 333 43.5

chloride benzoyD-benzene methallyl l-(2,4-dihydroxy-benzoyl)-3-(2'-hydroxy-4'-methallyloxy 333 47.9

chloride benzoyl)-benzene allyl I(2,4dihydroxy-benzoylr3-(2-hydroxy-4-allyloxy-benzoyl)- 333 48.3

chloride benzene 4-methvll-(Z,4-dihydroxy-benzoyl)-3-{2'-hydroxy'4-(4-methyl- 333 43.1

benzyl benzyloxy)-benzoyll-benzene chloride By using, instead of l,3-bis-(2,4-dihydroxy-benzoyl)- 45 benzene, the equivalent amount of 1,3-bis-(2,4- dihydroxy-benzoyl)-5-chlorobenzene, with otherwise the same procedure, the compounds listed in Table XIV are obtained.

Table XIV Alkylating Compound 80 Absorptivity agent nm a l-bromopropane l-(2,4-dihydroxy-benzoyl)-3'(2'- 334 46.7

hydroxy-4-propoxy)-5-chlorobenzene I-chloro- I-(2.4-dihydroxy-benzoyl)-3-(2' 335 43.7 pentane hydroxy-4'-pentoxy)-5-chlorobenzene l-chloro-3,3- l-(2,4-dihydroxy-benzoyl)'3-[2 334 42.6 dimethylbutane hydroxy-4'-(3".3"-dimethylbutoxy]- 5-chlorobenzene Lbromooctane l-(2.4-dihydroxy-benzoyl)-3-(2' 334 39.9

hydroxy-4'-octoxy)-5-chlorobenzene l-chlorotetra I-(2,4-dihydroxy-benzoyl)-3-(2'-hy- 335 35.0 decane droxy-4'-tetradecyl0xy)5-chlorobenzene l-bromoocta l-( 2,4-dihydroxy-benzoyl-3-2 -hy- 334 3 l .S decane droxy-4'-octadecyloxy)-5-chlorobenzene benzyl bromide l-(2,4-dihydroxy-benzoyl)-3-(2'-hy' 334 42.3

droxy-4-benzyloxy)-5-chlorobcnzenc methallyl l((2.4-dihydroxy-benzoyl)-3-[2"hy- 334 45.2 chloride droxy-4('2"-mcthylpropenoxy) ]-5-chloro-ben2ene' 21 22 EXAMPLE 16 d l-(2,4-dihydroxy-benzoyl)-3- 96 (2'-hydroxy-4-0ctadecy|oxy- 52.2 g of 1,3-bis-(2,4-dihydroxy-benzoyl)-benzene benzoyD-benzene are dissolved in a mixture of 75 ml of 2N sodium car- 8 'g'fi g i'g ifigzg fit 97 bonate solution and 32 ml of 5N sodium hydroxide sobenzgyhbgnzne Zy y lution. To the solution are then added at 60 70 5 f l-(2.4-dihydroxy-benzoyl)-3 93 within a quarter of an hour, whilst stirring is maintained, 19 g of dimethyl sulphate. Stirring proceeds for v g |a,4 dihyd i'nxy l7eIl ZOyU-3 96 a further 5 hours at 70 80 internal temperature and, (Zf-hydroxy-W-methnx after cooling, the reaction mixtue is poured into ice wah 92 ter. After acidification with dilute hydrochloric acid, the residue is filtered off, thoroughly washed with disbenzoyl)--chlorobenzene tilled water, dried and repeatedly treated in the hot gffi ygg xfjigifixl* 94 state with toluene and fullers earth. Any starting matebenzoy|) 5 chlordbenzefie rial present thereby remains undissolved. After concenj 1-(2,4-dihy xy 92 tration of the toluene solution, it is repeatedly recrysl5 tallised from toluene/acetonitrile and the l-(.2,4-

'dihydroxy-benzoyl)-3-(2'-hydroxy-4'-methoxy benzoyl)-benzene is obtained in the form of light yel- EXAMPLE 8 low crystals which melt at 180.

A 332 nm $19800.

mtead of dlmethyl Sulphate. the equivalent amou Difficultly inflammable liquid polyester resin is nt of diethyl sulphate is used, with otherwise the same I d 7 800 f f0 2 procedure the l-(2 4-dihydroxy-benzoyl)-3-(2'- 9 ymense at a l l O 5 percfmt by I eight ofa UV-absorber, given' n Table XVI, with l perhydrOxyA ethoxynbenzoylybenzene ls Obtamed' cent b wei ht of benzo l" eroxide to form 2 5 mm x =333nm =20100. Y E y P t o thick plates. The plates are afterwards cured at 120 EXAMPLE 17 Plates produced in this manner and exposed tolight A solution of 15 g of acetyl cellulose with, on averzi fi less browgmgthan platesfslmllarbi pose to ight ut produce without the a oremen age, 2.5-acetoxy groups per glucose unit, and 0.075 g d UV b b f UV-absorber iven th f ll w' T bl XV none 21 sot f m e O 0 mg a e The employed polyester resin was produced as fol- 0 acetone 15 smeared on to a glais plate to form lows: A mixture of 343g of maleic acid anhydride and g g g i 428 g of tetrachlorophthalic acid anhydride is added in ature and then in an bven at 6 0 S eciiiien s of ili es e portions at 80 toa mixture of 170 g of ethylene glycol 0 04 mm thick UV filters are ex 5 in d t and 292 g of diethylene glycol. After explusion of the i p0 or 9 meaair in the reaction vessel by nitrogen, the temperature sure the fastness to light ot the UV-absorbers, for 500 is raised over one hour to 0 then Over 9 hours to hollrs m.the g and tested 1th respect to 210 and thereafter maintained at this level for a furtheir residual UV-absorption. The obtained results are ther hour The mixture is the cooled to 0 the given m Table 4O sel is put under vacuum and the pressure slowly re Table XV duced to 100 Torr. These conditions are maintained until the acid number of the reaction mixture has fallen No. UV-Absorber Absorption still present in below 50. I

100 g of the thus obtained polyester are mixed with expogurg g of styrene and the mixture is polymerised under Rangel 300-340 nm the aforementioned conditions. Similar results are obtained if, instead of the tetraa 1(2,4-dihydroxy-benzoyl)-3- chlorophthalic acid, the equivalent amount of phthalic g g g fgg 's' acid anhydride is used, although, in this case, the resultb 1-(2,4-dil iydroxy-benzoyly} 96 ing polyester resin is not difficultly inflammable.

(2'-hydroxy-4'-hexoxy- If, in the above described process, the stryrene is reg g i l g fg 0 94 placed by methyl methacrylate, then plates are obc zi l f flfi i gg tained which are, in themselves, less prone to browning benzoyl)-benzene and which, moreover, are more easily stabilised.

Table XVI Nr, UV-Absorber 7:

Transmission Transmission loss with 440 nm with 440 nm before after 1000 hours exposure Fade-O-Meter exposure none 88 31 a l (2.4-dihydroxy-benzoyl)-3- 88 2.l

2-hydroxy-4'-butoxy-benzoyl)- benzene b l-(2,4-dihydroxy-benzoyl)-3- 88 2,4

(2 '-hydroxy-4 octoxy-benzoyD- benzene Table XVI Nr. UV-Absorber 7r Transmission Transmission loss with 440 nm with 440 nm before after I000 hours exposure FadeO-Meter exposure c I-(2,4-dihydroxy-benzoyl) 3- 87 1.9

(2"hydroxy-4-dodecyloxybenzoylhbenzene d I-(2,4-dihydroxy-benzoyl)-3- 88 2.5

(2-hydroxy-4 octadccyloxybenzoyl)-benzene e I-(2,4-dihydroxy-benzoyl)-3- 88 2.3

2-hydroxy-4-benzyloxybenzoyl)-benzene f I-(2,4-dihydroxy-benzoyl)-3- (2'-hydroxy-4"methoxy-benzoyl)- benzene EXAMPLE 19 100 parts of methacrylic acid methyl ester, 0.5 parts of a UV-asborber in Table XVII and 0.2 parts of lauroyl 20 peroxide are mixed together and polymerised at a temperature of 50-70 in the form of plates of 2 mm thick- As can be seen frorn the following table, such plates can be used as UV-filters.

EXAMPLE 20 Films are produced in the usual manner on a tworoller mill from a mixture of:

100 parts of suspension polyvinyl chloride (K-value 2.5 parts of a dialkyl tin mereaptide stabiliser (Advastab 17 M of the Deutschen Advance Production GmbI-I, Germany) 1.0 part of an epoxy stabiliser (Advaplast 39 of the aforementioned firm),

1.0 part of a wax, used as lubricant and processing auxiliary agent (Wax E of the firm Farbwerke H0- echst, Germany) and 0.2 parts of a UV-absorber in Table XVIII.

Specimens of these films are exposed for 2,000 hours in the Xenotest exposure apparatus and tested with respect to discolourations. The results are given in Table XVIII.

Table XVIII No. Uv Absorber Appearance of the exposed specimen without dark brown discolouration of the whole specimen a l-(2,4-dihydroxy-benzoyl)-3-(2-hydroxyslight yellow tint 4'-ethoxy-benzoyl)-benzene b I(2,4-dihydroxy-benzoyl)-3-(2'-hydroxyyellowish spots 4'-decyloxybenz0yl)-benzene at isolated places c I-(2,4-dihydroxy-benzoyl)-3-(2'-hydroxyyellowish spots 4-benzyloxy-benzoyl)benzene at isolated places If, instead of the aforementioned mixture, the following recipe is used:

parts of suspension polyvinyl chloride (K-value 1.2 parts of a barium-cadmium soap (Mark WS of the SA. Argus Chemical N.V., Belgium).

0.5 parts of an organic phosphite (Mark C of the above firm),

1.0 parts ofa wax (Wax E of the Farbwerke Hoechst,

Germany) and 0.2 parts of a UV-absorber in Table XIX,

with otherwise the same procedure, the results given in Table XIX are obtained:

Table XIX UV-Absorber' Appearance of the exposed specimen none severe browning of the whole specimen slight yellowing an isolated plnces somewhat yellowish octoxy-benzoyl )-benzenc yellowish dodecyloxy-benzoyl)-benzene EXAMPLE 21 100 parts of polyethylene with a density of 0.917 are homogeneously mixed at 180 in the Brabender- Plastograph with 0.5 parts of a UV-absorber in Table XX and 0.5 parts of 3-(3,5-di-t.butyl-4-hydroxyphenyl)-propionic acid octadecyl ester. The thus obtained mixture is pressed in a platen press at 165 to form -1 mm thick plates.

After weathering, these plates exhibit, in the case of bending around 90, appreciably less proneness to brittleness than plates without the addition of the additives in Table XX.

Table XX No. UV'Absorber a l-(2,4-dihydroxy-benzoyl)-3-(2-hydroxy-4 hexoxybenzoyl)-benzene b l-(2,4-dihydroxybenzoyl) 3-(2 -hydroxy-4 '-octoxybenzoylJ-benzene c. I l-(2,4-dihydroxy benzoyl)-3-(2'-hydroxy-4dodecyloxybenzoylJ-benzene d l-(2,4-dihydroxy-benzoyl)-3-(2 '-hydroxy-4octadecyloxybenzoy1)-benzene I If, instead of the aforementioned phenolic antioxidant, an equal amount of 3,5-di-t.butyl-4-hydroxybenzyl-di-octadecyl-phosphonate is used, with otherwise the same procedure, similar results are obtained.

XAMPLE 22 100 parts of polypropylene with a density of 0.90are homogeneously mixed at 220 in the Brabender-' Plastograph with 0.5 parts of a UV-absorber in Table XXI, 0.2 parts of .bis-(5-t.butyl-4-hydroxy-2-methylphenyl)-sulphide, 0.2 parts of dilauryl thiodipropionate.

and 0.2 parts of triactadecyl p-hosphite. The .thus obtained mixture is pressed in a platen press at 180 to.

form plates of 1 mm thickness.

After weathering, these plates exhibit, in the case of bending around 90, appreciably less proneness to brittleness than plates produced otherwise in the same manner, but without addition of the protective agent against light rays given in Table XXI.

Table XXI No. UV-Absorber a 1-(2,4-dihydroxy-benzoyl)-3-(2 '-hydroxy-4 -pentoxybenzoyl)- benzene b l-(2.4-dihydroxy-benzoyl)-3-(2 -hydroxy-4-decyloxybenzoyh-benzene d l(2.4-dihydroxy-benzoyl)-3-(2 -hydroxy 4 '-octadecyloxybenzoyll-benzene benzoyU-benzene EXAMPLE 23 100 parts of polystyrene granulate are mixed dry with 0.3 parts of a protective agent against light rays, listed in Table XXII, and 0.1 parts of 2,4,6-tri-t.butyl-phenol and the mixture is sprayed with an injection moulding" machine to form 2 mm thick plates.

The obtained plates are exposed for 1,000 hours in.

the Xenotest apparatus and subsequently the yellowing of the plates is determined by means of the yellowing.

factor in the following manner:

Y.F. [AT(420) 4 AT(680)]/[T(560)]100,

whereby AT represents the transmission loss occurring during exposure with the wave-lengths 420 and 680 nm, and T (560) represents the transmission value in percent of the unexposed specimen in the case of 560 Table XXII No. UV-Absorber V.F.

without 15 a l (2,4-dihydroxy-benzoyU-S-(Z-hydroxy4'- 1.9

hexoxy-benzoyD-benzene b l-(2,4-dihydroxy-benzoyl)-3(2'-hydroxy-4- 2. octyloxy-benzoyl)benzene c l-(2,4-dihydroxy-benzoyl)-3-(2-hydroxy-4- 2.4

dodecyloxy-benzoyl) benzene d l-(2,4-dihydroxy-benzoyl)-3-(2'-hydroxy-4- 2.3

benzyloxy-benzoylJ-benzene EXAMPLE 24 Bleached maple-veneer is coatedwith a wood varnish having the following composition:

15.0 parts by weight of cellulose acetate (of the Firma Bayer in Leverkusen. Germany) having ca. 56% acetic acid content.

parts by weight of dimethyl glycol phthalate. part by weight of benzene.

parts by weight of methyl alcohol. parts by weight of toluene and parts by weight of ethyl acetate.

COL):

The natural yellowing of the wood is retarded by this varnish.

XAMPLE 2s A cosmetic protective agent against light rays is obtained as follows:

5 parts of white ceresine wax,

parts of white petrolatum,

19.5 parts of white mineral oil, 15 parts of lanoline anhydrous 2 parts of 1-(2,4-dihydroxy"benzoyl)-3-(2'-hydroxy 4'-ethoxy-benzoyl)- benzene, 36 parts of water.

0.5 parts of perfume.

The ceresine, petrolatum and lanoline are melted to gether and the protective agent against light rays dissolved in the melt. The mineral oil is then added at and, subsequently. the water is slowly stirred in at the same temperature. Stirring is continued until the temperature has fallen below 50, whereupon the perfume is added.

EXAMPLE 26 1,3-bis-(2"-hydroxy-4'-octoxybenzoyl )-benzene. I 

2. The compound 1,3-bis-(2''-hydroxy-4''-octoxy-benzoyl)-benzene.
 3. The compound 1,3-bis-(2''-hydroxy-4''-dodecyloxy-benzoyl)-benzene.
 4. The compound 1,3-bis-(2''-hydroxy-4''-(2''''-methylpropenoxy) -benzoyl)-benzene.
 5. The compound 1,3-bis-(2''-hydroxy-4''-octa-decyloxy-benzoyl)-benzene.
 6. The compound 1,3-bis-(2''-hydroxy-4''-(3,3-dimethylpropyloxy) benzoyl)-benzene.
 7. The compound 1,3-bis-(2''-hydroxy-4''-benzyloxybenzoyl)-benzene.
 8. The compound 1,3-bis-)2-hydroxy-4''-(4-tert-butylbenzyloxy) benzoyl)-benzene. 